Excitation-emission-lifetime analysis of multicomponent systems—III. Platinum, palladium and rhodium porphyrins

Russell, Michael D.; Gouterman, Martin; Zee, James A. van

doi:10.1016/0584-8539(88)80003-5

Cited by 20 publications

(11 citation statements)

References 6 publications

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“…The iterative procedure therefore converges in only one step. The matrices U I and V , were then to calculate C, in (8) To resolve the mixture we can take any two of these matrices and diagonalize them according to (11) to obtain P and Q, and then calculate the resolved spectra according to (9). The uncorrected matrix correlations (UMC)3 for the resolved spectra corresponding to different pairs of C; and C, are listed in Table 1.…”

Section: Spectral Deconvolution and Lifetime Calculationmentioning

confidence: 99%

“…Given P and Q, we can use (9) to obtain the excitation and emission spectra for the K compounds in the mixture. To get the fluorescence lifetimes 7 k we need values for the df,k also.…”

Section: Spectral Deconvolution and Lifetime Calculationmentioning

confidence: 99%

“…The approach was later extended by Russell and Gouterman to the analysis of excitation-emission-lifetime arrays in which the time decay profile of fluorescence following pulsed excitation was used as the third dimension. 7 - 9 The methodology, however, requires good initial guesses for the 0886-9383/90/0IOOl5-14$07.00 0 1990 by John Wiley & Sons, Ltd. unknown spectra, and the convergence of the algorithm depends heavily on the initial guesses. It also requires that the decay profiles be measured at multiple time points to obtain good estimates for the lifetimes.…”

Section: Introductionmentioning

confidence: 99%

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Resolution of multicomponent fluorescent mixtures by analysis of the excitation–emission–frequency array

Burdick

McGown

et al. 1990

Journal of Chemometrics

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SUMMARYFluorescence lifetime provides a third independent dimension of information for the resolution of total luminescence spectra of multicomponent mixtures. The incorporation of this parameter into the excitation-emission matrix (EEM) by the phase modulation technique results in a three-dimensional excitation-emission-frequency array (EEFA). Multicomponent analysis based on the three-dimensional EEFA brings a qualitative change for the resolved spectra, i.e. individual spectra can be uniquely resolved, which is impossible with any two-dimensional analysis. In this paper we present a method for analyzing the EEFA. We show mathematically that with the three-dimensional analysis of the EEFA individual spectra and lifetimes can be obtained. Our algorithm is developed in mathematical detail and is demonstrated by its application to a two-component mixture.

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Section: Spectral Deconvolution and Lifetime Calculationmentioning

confidence: 99%

“…Given P and Q, we can use (9) to obtain the excitation and emission spectra for the K compounds in the mixture. To get the fluorescence lifetimes 7 k we need values for the df,k also.…”

Section: Spectral Deconvolution and Lifetime Calculationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Resolution of multicomponent fluorescent mixtures by analysis of the excitation–emission–frequency array

Burdick

McGown

et al. 1990

Journal of Chemometrics

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“…These two matrices may be generated using a two-component Tucker-1 model for R (equation ( 5 ) ) for the ( z , ) space: (17) s,= c W p k R k (18) …”

Section: Three or More Variables In Third Ordermentioning

confidence: 99%

Tensorial resolution: A direct trilinear decomposition

Sanchez

Kowalski

1990

Journal of Chemometrics

429

190

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SUMMARYModern instrumentation in chemistry routinely generates two-dimensional (second-order) arrays of data. Considering that most analyses need to compare several samples, the analyst ends up with a threedimensional (third-order) array which is difficult to visualize or interpret,with the conventional statistical tools.Some of these data arrays follow the so-called trilinear model,These trilinear arrays of data are known to have unique factor analysis decompositions which correspond to the true physical factors that form the data, i.e. given the array R, a unique solution can be found in many cases for each order X , Y and Z . This is in contrast to the well-known second-order bilinear data factor analysis, where the abstract solutions obtained are not unique and at best cannot be easily compared with the underlying physical factors owing to a rotational ambiguity. Trilinear decompositions have had the disadvantage, however, that a non-linear optimization with many parameters is necessary to reach a least-squares solution. This paper will introduce a method for reducing the problem to a rectangular generalized eigenvalue-eigenvector equation where the eigenvectors are the contravariant form (pseudo-inverse) of the actual factors. It is shown that the method works well when the factors are linearly independent in at least two orders (e.g. X,, and Y,, are full rank matrices).Finally, it is shown how trilinear decompositions relate to multicomponent calibration, curve resolution and chemical analysis.

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“…Inefficient transfer of energy may be the result of (a) a large distance between the potential donor and the potential acceptor, (b) a low value of the average molar extinction coefficient of the acceptor in the region of overlap between its absorption spectrum and the fluorescence spectrum of the donor, (c) a low value of the fluorescence quantum yield of the donor (in the absence of energy transfer), or (d) an unfavorable orientation between the transition dipole moments of the donor and the acceptor (26). The incorporation of energy transfer into this analysis is a challenging task, one that has yet to be accomplished by any of the currently available methodologies for analyzing spectral data (8)(9)(10)(11)(12)(13)(14)(15)(16). Work in progress in our laboratory is attempting to do that.…”

Section: Multicomponent Mixturesmentioning

confidence: 99%

Global analysis of steady-state polarized fluorescence spectra using trilinear curve resolution

Phillips

Georghiou

1993

Biophysical Journal

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Global analysis using trilinear curve resolution is described and shown to be a powerful method for the resolution of polarized fluorescence data arrays, in which the measured fluorescence intensity is a separable function of polarization orientation, excitation wavelength, and emission wavelength. This methodology is applicable to mixtures the components of which have linearly independent excitation and emission spectra and distinct anisotropies. Normalized excitation and emission spectra of individual components can be uniquely determined without prior assumptions concerning spectral shapes (e.g., sum of Gaussians) and without the uncertainties inherent in bilinear techniques such as principal component analysis or factor analysis. The normalized excitation and emission vectors are combined with the total absorption spectrum of the multicomponent mixture to compute absolute absorption and emission spectra. The precision of this methodology is evaluated as a function of noise, overlap, relative intensity, and anisotropy difference between components using simulated mixtures of the DNA bases. The ability of this method to extract individual spectra from steady-state fluorescence data arrays is illustrated for mixtures containing two and three components.

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Excitation-emission-lifetime analysis of multicomponent systems—III. Platinum, palladium and rhodium porphyrins

Cited by 20 publications

References 6 publications

Resolution of multicomponent fluorescent mixtures by analysis of the excitation–emission–frequency array

Resolution of multicomponent fluorescent mixtures by analysis of the excitation–emission–frequency array

Tensorial resolution: A direct trilinear decomposition

Global analysis of steady-state polarized fluorescence spectra using trilinear curve resolution

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